Asymmetrical mannich base derivatives and the production and uses thereof

Abstract

Compounds are described in which a polyamine moiety is linked to a phenolic moiety by a Mannich base linkage involving one of the amino groups of the polyamine moiety, and in which an aminoalkylene-poly(oxyalkylene) moiety is linked to the phenolic moiety by a Mannich base linkage involving an amino group of the alkylene-poly(oxyalkylene) moiety. Compounds of this type have been found to be highly effective in controlling the formation of intake valve deposits in internal combustion engines.

I claim: 
     
       1. A compound in which a polyamine moiety is linked to a phenolic moiety by a Mannich base linkage involving one of the amino groups of the polyamine moiety, and in which an aminoalkylene-poly(oxyalkylene) moiety is linked to said phenolic moiety by a Mannich base linkage involving an amino group of the alkylene-poly(oxyalkylene) moiety. 
     
     
       2. A compound according to claim 1 wherein said polyamine moiety is linked by the Mannich base linkage to an ortho position of said phenolic moiety, and said aminoalkylene-poly(oxyalkylene) moiety is linked by the Mannich base linkage to an ortho position of said phenolic moiety. 
     
     
       3. A compound according to claim 2 wherein said phenolic moiety is derived from a mononuclear monohydric phenol. 
     
     
       4. A compound according to claim 3 wherein said phenolic moiety has a hydrocarbyl substituent in the para position. 
     
     
       5. A compound according to claim 4 wherein said hydrocarbyl substituent is a branched chain dodecyl or a branched chain nonyl group. 
     
     
       6. A compound according to claim 4 wherein said hydrocarbyl substituent is derived by alkylating said mononuclear monohydric phenol with an oligomer or polymer of propene having from 4 up to about 100 propene units per molecule. 
     
     
       7. A compound according to claim 4 wherein said oligomer or polymer is a polypropene having a molecular weight by vapor phase osmometry in the range of about 800 to about 1000. 
     
     
       8. A compound according to claim 2 wherein said phenolic moiety is derived from a dinuclear dihydric bisphenol. 
     
     
       9. A compound according to claim 8 wherein said bisphenol is Bisphenol-A. 
     
     
       10. A compound of the formula:   A--L--R--L'--R'     wherein A is a polyamine group having 2 to 10 nitrogen atoms, and is derived from a polyamine; R is a phenolic group derived from a hydroxyaromatic compound; R' is an alkylenepoly(oxyalkylene) group derived from an amino-substituted alkylenepoly(oxyalkylene) compound, and in which the alkylene groups can be the same or different and contain from 2 to 20 carbon atoms each; L is a methyleneamino linkage in which the amino nitrogen atom is one of the nitrogen atoms of the polyamine group; and L' is a methyleneamino linkage in which the nitrogen atom of L' is a nitrogen atom of an amino substituent in the alkylenepoly(oxyalkylene) group.   
     
     
       11. A compound in accordance with claim 10 wherein the hdroxyaromatic reactant from which R is derived is a monoalkylated phenol in which the alkyl substituent is derived from a polymer of propene having a molecular weight by vapor phase osmometry in the range of about 800 to about 1000. 
     
     
       12. A compound in accordance with claim 11 wherein R' is an amino-substituted alkylenepoly(oxyalkylene) group derived by removal of one amino hydrogen atom from a polyamino-substituted alkylenepoly(oxyalkylene) reactant of the formula:   H.sub.2 N-alkylene-(O-alkylene).sub.x --NH.sub.2     wherein the alkylenes can be the same or different and contain from 2 to 5 carbon atoms each, and x is an average number in the range of about 10 to about 80.   
     
     
       13. A compound in accordance with claim 11 wherein R' is an amino-substituted alkylenepoly(oxyalkylene) group derived by removal of one amino hydrogen atom from a polyamino-substituted alkylenepoly(oxyalkylene) reactant of the formula:   H.sub.2 N-alkylene-(O-alkylene).sub.y --NH--CO--NH--(O-alkylene).sub.z -alkylene-NH.sub.2     wherein the alkylenes can be the same or different and contain from 2 to 5 carbon atoms each, and y and z can be the same or different and each is an average number in the range of from 2 to 20.   
     
     
       14. A compound in accordance with claim 11 wherein R' is a polyamino-substituted alkylenepoly(oxyalkylene) group derived by removal of one amino hydrogen atom from a polyamino-substituted alkylenepoly(oxyalkylene) reactant of the formula: ##STR5## wherein the alkylenes can be the same or different and contain from 2 to 5 carbon atoms each, Q is the hydrocarbyl residue of a triol, and a, b and c can be the same or different and each is an average number in the range of from 1 to about 35, the sum of a, b and c being in the range of about 5 to about 100. 
     
     
       15. A compound in accordance with claim 11 wherein R' is an amino-substituted alkylenepoly(oxyalkylene) group derived by removal of one amino hydrogen atom from the amino-substituted alkylenepoly(oxyalkylene) reactant of the formula:   H.sub.2 N-alkylene-(O-alkylene).sub.x --R"     wherein the alkylene groups can be the same or different and contain from 2 to 5 carbon atoms each, x is an average number in the range of about 10 to about 60, and R" is a hydrocarbyl group of up to about 18 carbon atoms.   
     
     
       16. A compound in accordance with claim 15 wherein the alkylene groups are a combination of ethylene and methylethylene groups, x is an average number in the range of about 10 to about 40, and R" is an alkyl group of up to about 12 carbon atoms. 
     
     
       17. A compound according to claim 16 wherein said amino-substituted alkylenepoly(oxyalkylene) reactant has a molecular weight in the range of about 1000 to about 2000 and wherein R" is methyl. 
     
     
       18. A compound according to claim 11 wherein the polyamine moiety is derived from a mixture of straight chain, branched chain and cyclic ethylene polyamines having about 2 to about 10 nitrogen atoms in the molecule. 
     
     
       19. A compound in accordance with claim 11 wherein the polyamine moiety is derived from diethylene triamine, triethylene tetramine or N-aminoethylpiperazine. 
     
     
       20. A compound according to claim 11 wherein the polyamine moiety is derived from N-decyloxy-1,3-propanediamine or N-tridecyloxy-1,3-propanediamine. 
     
     
       21. A compound formed by reacting in the first stage a phenolic compound having at least two unsubstituted ortho positions or at least one unsubstituted ortho and one unsubstituted para position with an aldehyde and either (i) a polyamine having at least one primary or secondary amino group capable of undergoing a Mannich condensation reaction with said phenolic compound, or (ii) an alkylene-poly(oxyalkylene) compound having at least one primary or secondary amino group capable of undergoing a Mannich condensation reaction with said phenolic compound in proportions to form an intermediate Mannich condensation product enriched in mono-substituted Mannich condensation product, and then reacting said intermediate Mannich condensation product in a second stage Mannich condensation reaction with an aldehyde and whichever of (i) and (ii) was not used in the first stage. 
     
     
       22. A compound according to claim 21 wherein the aldehyde used in both said reactions is formaldehyde or a formaldehyde-producing reagent, wherein the polyamine used has at least one terminal primary amino group, and wherein the alkylene-poly(oxyalkylene) compound used has at least one terminal primary amino group. 
     
     
       23. A compound according to claim 22 wherein (i) is diethylene triamine, triethylene tetramine or N-aminoethylpiperazine, and (ii) is a compound of the formula:   H.sub.2 N-alkylene-(O-alkylene).sub.x --R"     wherein the alkylene groups can be the same or different and contain from 2 to 5 carbon atoms each, x is an average number in the range of about 10 to about 60, and R" is a hydrocarbyl group of up to about 18 carbon atoms.   
     
     
       24. A compound in accordance with claim 23 wherein the alkylene groups are a combination of ethylene and methylethylene groups, x is an average number in the range of about 10 to about 40, and R" is an alkyl group of up to about 12 carbon atoms. 
     
     
       25. A compound according to claim 24 wherein (ii) has a molecular weight in the range of about 1000 to about 2000 and wherein R" is methyl. 
     
     
       26. A compound according to claim 22 wherein (i) is N-decyloxy-1,3-propanediamine or N-tridecyloxy-1,3-propanediamine, and (ii) is a compound of the formula:   H.sub.2 N-alkylene-(O-alkylene).sub.x --R"     wherein the alkylene groups can be the same or different and contain from 2 to 5 carbon atoms each, x is an average number in the range of about 10 to about 60, and R" is a hydrocarbyl group of up to about 18 carbon atoms.   
     
     
       27. A compound in accordance with claim 26 wherein the alkylene groups are a combination of ethylene and methylethylene groups, x is an average number in the range of about 10 to about 40, and R" is an alkyl group of up to about 12 carbon atoms. 
     
     
       28. A compound according to claim 27 wherein (ii) has a molecular weight in the range of about 1000 to about 2000 and wherein R" is methyl. 
     
     
       29. A process for the preparation of a compound of claim 1 which comprises reacting in a first stage a phenolic compound having at least two unsubstituted ortho positions or at least one unsubstituted ortho and one unsubstituted para position with an aldehyde and either (i) a polyamine having at least one primary or secondary amino group capable of undergoing a Mannich condensation reaction with said phenolic compound, or (ii) an alkylene-poly(oxyalkylene) compound having at least one primary or secondary amino group capable of undergoing a Mannich condensation reaction with said phenolic compound in proportions to form an intermediate Mannich condensation product enriched in mono-substituted Mannich condensation product, and then reacting said intermediate Mannich condensation product in a second stage Mannich condensation reaction with an aldehyde and whichever of (i) and (ii) was not used in the first stage. 
     
     
       30. A process according to claim 29 wherein (ii) has the formula:   H.sub.2 N-alkylene(O-alkylene).sub.n --NH.sub.2     wherein the alkylenes can be the same or different and contain from 2 to 20 carbon atoms each, and n is a number in the range of 2 to 150.   
     
     
       31. A process according to claim 29 wherein (ii) has the formula:   H.sub.2 N-alkylene-(O-alkylene).sub.x --R"     wherein the alkylene groups can be the same or different and contain from 2 to 5 carbon atoms each, x is an average number in the range of about 10 to about 60, and R" is a hydrocarbyl group of up to about 18 carbon atoms.   
     
     
       32. A distillate fuel for use in an internal combustion engine containing a compound in accordance with claim 1 in an amount at least sufficient to minimize induction system deposit formation. 
     
     
       33. A gasoline fuel for use in an internal combustion engine containing a compound in accordance with claim 23 in an amount at least sufficient to minimize induction system deposit formation. 
     
     
       34. A gasoline fuel for use in an internal combustion engine containing a compound in accordance with claim 24 in an amount at least sufficient to minimize induction system deposit formation. 
     
     
       35. A gasoline fuel for use in an internal combustion engine containing a compound in accordance with claim 25 in an amount at least sufficient to minimize induction system deposit formation. 
     
     
       36. A gasoline fuel for use in an internal combustion engine containing a compound in accordance with claim 26 in an amount at least sufficient to minimize induction system deposit formation. 
     
     
       37. A gasoline fuel for use in an internal combustion engine containing a compound in accordance with claim 27 in an amount at least sufficient to minimize induction system deposit formation. 
     
     
       38. A gasoline fuel for use in an internal combustion engine containing a compound in accordance with claim 28 in an amount at least sufficient to minimize induction system deposit formation. 
     
     
       39. A fuel in accordance with claim 32 additionally containing in the range of from about 0.5 to 5 parts by weight of carrier fluid per part by weight of said compound. 
     
     
       40. An additive composition for addition to fuel for internal combustion engines which comprises a compound in accordance with claim 1 and in the range of from about 0.5 to 5 parts by weight of carrier fluid per part by weight of said compound. 
     
     
       41. A method of minimizing induction system deposits in an internal combustion engine which comprises operating said engine on a distillate fuel containing a compound in accordance with claim 1 in an amount at least sufficient to minimize induction system deposits in said engine. 
     
     
       42. A method in accordance with claim 41 wherein said engine is a gasoline engine, wherein said distillate fuel is a gasoline fuel, and wherein at least intake valve deposits are minimized in said engine. 
     
     
       43. A method in accordance with claim 42 wherein said gasoline fuel additionally contains in the range of from about 0.5 to 5 parts by weight of carrier fluid per part by weight of said compound.